Permanent waving compositions and methods



Patented Dec. 4, 1951 PERMANENT WAVING COMPOSITIONS AND METHODS Everett Goodrich McDonough, Yonkers, N. Y.

No Drawing. Application November 1, 1949, Serial No. 124,940

(Cl. 132'l) 13 Claims. 1

This invention relates generally to the art of permanently altering the physical form or shape of hair, and, more particularly, to the art of permanently waving hair. The present application is a continuation-in-part of my copending application Serial No. 398,235, filed June 16, 1941.

It is known that the physical form or shape of hair can be permanently altered without injury to the hair structure by utilizing three forces, namely, a mechanical force, a chemical or softening force, and a fixing or setting force. More particularly, in permanent waving the mechanical force is set up by winding the hair in curls as on mandrel's'. A chemical medium is then (or previously) "applied to create the chemical or softening force'adapted to place the wound tresses in condition to be permanently molded and altered to their new form as determined by the winding.

Finally, means are utilized to fix the wound tresses in their new form, which latter means may consist of an application of heat, generated electrically, chemically or in any other way followed by cooling or a second chemically reactive force to neutralize the chemical waving medium.

The present invention is concerned with the chemical medium which provides the chemical or softening force above referred to, this being identified hereinafter for descriptive purposes only as the waving solution, and comprising an aqueous solution containing the waving agent or agents.

Heretofore, the practice has been to use a waving agent for such solutions which is an alkaline material, for example, borax, various carbonates and phosphates of alkaline materials, ammonia and ammonium salts, such as the carbonates. Furthermore, soluble sulfites of alkalies and ammonia have been utilized for the waving agent, and sulfides have also been provided for this purpose.

However, with respect to the sulfites and to all other heretofore utilized waving agents excepting sulfides, relatively high concentrations are necessary in order to obtain any satisfactory permanent wave in the hair. Especially with fine hair, there is difllculty in providing a suitable waving solution for obtaining an altered form or shape for the hair which can be termed permanent.

I have found that there is a limiting concentration of these materials above which either hair destruction or injury occurs with less satis-,- factory wave. It is probably this upward limiting effect on concentration of these waving agents that make it impossible to obtain satisfactory results in a short time where the hair is set'by a chemical force, for the solution containing these waving agents must be left in contact with the hair for periods ranging from four to twenty-four hours before a satisfactory wave may be obtained.

The sulfides do not require as long a time nor need quite as great a concentration as the sulfites and a satisfactory solution may be made therefrom for most types of hair and even fine hair under some conditions, but many disadvantages appear when using sulfides, the first of which is the characteristic odor of rotton eggs possessed by such sulfides resulting from generation and liberation of free hydrogen sulfide by hydrolysis. All attempts to mask this odor result in failure and the use of-heavy perfumes only serve to minimize the objectionable odor. Secondly, these sulfides have a tendency to cause tarnishing and blackening on metal, particularly jewelry, silverware, and the like, which is a further objection to their use in the waving lotion. Furthermorethe disgusting odor which accompanies the use of such hydrogen sulfide salts is toxic to breathe and although/normally the amount of hydrogen sulfide produced thereby is not dangerous, when in a confined booth or room such as a. beauty shop cubicle often used in hair waving establishments, the concentration of the gas may become so high as to seriously affect both operator and patron, unless expensive ventilating equipment is installed and maintained to remove this gas.

Thus, it will be seen that, while these sulfides are satisfactory in use in waving solutions from the point of view of performance or results in the finished permanent wave, they are wholly unsatisfactory becauseef the combined effect of toxicity, nauseating odor, and metallic coating effect.

More specifically, one of the best waving agents known for use when carrying out a permanent change of form or shape of the hair is ammonium hydrogen sulfide; but despite its relatively greater waving power, the use thereof is limited by liberation of hydrogen sulfide gas, together with ammonia gas. These evolved gases make this compound very objectionable and perhaps dangerous, unless special precautions to remove the vapors, for instance, by suction ventilators, are taken.

Another objection to use of ammonium hydrogen sufide and other sulfides is that the hairtends to retain the sulfide in spite of repeated rinsings even when using a chemical setting solution. The result is a mal-odor to the hair, particularly on each re-wetting. More important, however, is the fact that this retention by the 3 hair of the sulfide affords a continuous relaxing effect on the permanent wave with the result that the wave becomes less tight with each re-wetting.

It is the general objective of this invention to provide an agent for use in altering the permanent form or shape of hair which will be similar in its effect-to that of the sulfides referred to above and yet will notfpossess the great disadvantages mentioned.

It is a further object of this invention to provide a lotion for the permanent waving of hair containing'an entirely novel ingredient as the waving agent which will give the solution a wide range of adaptability for permanent waving of any type or texture of hair.

It is a further object of this invention to provide a-non-odorous, non-toxic hair waving solution adapted to more rapidly and more successfully place hair in a condition to be altered in form or shape permanently, irrespective of whether cooling subsequent to heating or chemical means is used after applying the waving solution in order to fix the hair in its new configuration.

It is a further object of this invention to provide a waving solution suitable for that type of permanent waving of hair which utilizes a chemical action for the fixing of the hair in its wound form, such waving solution containing a waving agent as powerful, rapid and satisfactory as ammonium hydrogen sulfide, but free from the limitations of ammonium hydrogen sulfide, particularly the bad odor and toxicity. Y

It is a further object of this invention to provide a waving solution powerful enough to wave hair without the need of added heat and which can be neutralized or completely removed by water alone; or, in other words, the wave can be fixed in the hair by washing out the waving agent with water alone.

By this invention there is provided an agent for use in the permanent reforming of hair which is fast in action, satisfactory iniuse for all types of hair and yet is free from objectionable odors or toxicity or the like.

I have discovered that I can obtain these objects by providing as a waving agent a mercaptan, or a mixture of mercaptans, whether the fixing of the new form for the hair be by cooling subsequent to heating, or by using chemical rinses or by any other method, and, further, that an eifective waving solution can be obtained by proper formulation including a mercaptan in water. The mercaptans are represented by the formula R-SH where R is an organic group such as the ethyl group in H H no-o-sn H n Ethyl mercaptan or the benzyl group in [Benzyl mercaptan Such simple mercaptans will function adequately as waving agents, but they stil have the disadvantage of sulfides, such as ammonium hydrogen sulfide as far as bad odor is concerned.

I have discovered that badodor, and other disadvantages can be entirely obviated by having the molecule contain other groups which are carefully selected. as hereinafter set forth, to give the optimum desired results, Forinstance, the

mercaptan molecule may contain polar groups, which in turn may be either acidic or alkaline groups. Examples of compounds and groups of compounds belonging under the general heading of polar acidic substituted mercaptans are: mercaptans containing the carboxylic groups, as, for example, the simple mercapto-alkanoic acid. mercapto-acetic acid (thioglycollic), mercaptans containing sulfonic groups, as, for example, mercapto-ethyl ulfonic. Other acidic groups are nitro, chloro, r. other halogenated groups, sulfonic, sulfate. It is to be noted that any homo: logues could be used and that cyclic, or benzenoid groups may be included-also derivatives of these compounds, such as salts, esters, amides, and the like. Examples of polar alkaline substituted mercaptans are: Mercaptan containing amino groups, which may be primary, as, for example, B-amino ethyl mercaptan, or, secondary, as, for example, B-mercapto-ethyl methyl amine or tertiary, as, for example, B-mercapto ethyl dimethyl amine. Other alkaline groups are imines and nitrogen heterocyclic compounds. It is to be noted that any homologues could be used and that cyclic, or benezenoid groups may be included-also derivatives of these compounds, such as salts, nitrogen derivatives, amides, and the like.

n the other hand, the molecule may contain non-polar groups. .An example of a mercaptan containing the non-polar hydroxyl group is the simple mercanto-carbinol compound, B-mercapto-ethyl alcohol. An example of mercaptans containing non-polar aldehyde groups is the simple mercapto-carbinal, mercapto acetaldehyde. An example of mercaptan containing non-polar ketone groups is the simple mercaptocarbonyl, mercapto-di-methyl ketone. An example of mercaptan containing ester groups is the simple mercapto-ester, mercapto ethyl acetate. As an example of mercaptan containing ether groups is the simple mercapto-ether, B- mercapto-di-ethyl ether. Homologues, cyclic or benzenoid and other derivatives of these com- 5 pounds could be used- Many other compounds could be listed such as the mercaptan containing more than one substituted group such as, for example, 3 amino-2 hydroxy propyl mercaptan.

Many other mercaptan compounds could be included under the groups above and the following lists are given to show the wide variety or mercaptans which may be used and to show that mercaptans having poly mercaptoand poly sub- 55 stituted groups may be used: 1, Thioglycerol,

mono-, di-, or polythio-polyhydric alcohols, e. g.,

trithio hexitols, monoand polythio-polyoxyethylene glycols (e. g., tetra glycol dimercaptan) 2, mercapto-ethylhydroxy ethylamine, tri-mer- 60 capto-ethyl amine; 3, mono-, dl-, and polythiopolyhydroxyacids; 4, mercapto diand polycarboxylic acids, mono-, diandtrithio mucic acids, mono-, dimercapto succinic acid, thiocitric acid, mercaptoamino acids; 5, alpha mercapto-methyl 65 furane, thlophene, pyrrole, pyrimidine, thiofufuralcohol; 6, mercapto alkyl pseudo thioureas; '7,

mercaptoalkylureas and thioureas; 8, mercaptoethyl urethane, mercapto-ethylacetamide, mercapto ethyl guanidine, mercaptoalkyl betaines 7 and taurines.

I have discovered that all of the materials mentioned above function satisfactorily as hair waving agents when used in solutions. The concentration is usually less than 15%. I have 75 found'that the mercaptans are especially-eflective when the pH range is from 7.0 to 10.0, the preferred pH being about 9.2.

I have found that all alkaline materials are satisfactory for adjusting these pH, but that particularly effective with less hair destructive effect are bases having a dissociation constant less than l0- and preferably about In the cold" waving process also I have found the volatile bases, such as ammonia, methylamine, and ethylamine are to be preferred with the mercaptans, since at the same pH value and mercaptan concentration solutions containing these volatile bases give tighter waves. Ammonia, therefore, is particularly to be preferred with the mercaptans since its ionization constant is satisfactory, its odor blends pleasantly with the mercaptans and it has a relatively non-irritating action in the desired pH range of 7.0 to 10.0.

This pH range is particularly critical when the waving agent is used for that type of waving employing a chemical setting agent. as in the socaller cold waving method, since in that system the necessary requirement of speed without hair destruction demands a high concentration of the waving agent in the waving solution. If the pH value is not high enough slow waving action will result and if too high the hair will be destroyed or badly damaged. While with sulflte a shorter waving time may require a pH of 10 or above, with these more powerful waving agents, the use of pHs higher than 9.5 must be watched very carefully for with pH of 10 or above, hair destruction or iniury may occur before a satisfactory wave is obtained.

It is to be noted that organic sulfides and dlsulfldes are not effective waving agents.

I have discovered that whereas all the mercaptans function very effectively in permanent waving where the final set is accomplished by heating and then cooling, when used in the so-called cold waving" method requiring a chemical setting solution, unusual and startling differences from the prior art become apparent.

Ihave discovered that from the point of view of efficiency of waving action, the least effective compounds are the mercaptans containing polar acid groups such, for example, as mercaptoacetic acid. For example, even when using twice the concentration of mercapto acetic acid at the optimum pH, the wave obtained is not as good as when using a mercaptan having non-polar groups such as glyceryl mono mercaptan.

Furthermore, I have found that mercaptans containing polar groups are difdcult to remove from the hair and whenever the hair becomes damp, for instance, in bathing, shampooing, or at sports such as skiing, the residual odor tends to offend. This is most observable with mercaptans containing polar alkaline groups such as B-amino ethyl mercaptan.

This odor effect is thus of tremendous importance, not only during the processing of the wave, but for a long time after the wave has been given. I have found that whereas certain groups such as polar groups tend to reduce the vapor pressure of the mercaptan and thus make the resulting mercaptan less objectionable, nevertheless the malodor, although much fainter, tends to persist. I have discovered, however, that while the nonpolar groups may be less effective in reducing the vapor pressure yet they change the resulting odor by the sweetening action of their groups. For

sweeter than the propyl mercaptan. Also, other non-polar groups, such as ethers, aldehydes, ketones and esters are effective, as is illustrated by the effect of the ether linkage of the following related compounds. Increasingly pleasant to smell are diglycol di-mercaptan, triglycol dimercaptan, tetraglycol dimercaptan.

I have also discovered that as the molecular weight increases, the mercaptan becomes less eiiective as a waving agent, particularly if the increase is due to a polar acid group. For gxample, B-amino ethyl mercaptan (molecular weight 77) is far more efficient as a waving agent than cysteine (molecular weight 121) which is molecularly heavier and contains the additional polar carboxyl group.

I have discovered that by far the best waving agents within the scope and spirit of this invention, from every standpoint, are the ercaptans containing non-polar groups, and articularly water-solubilizing groups, such as the hydroxy and ether groups thereof. For example, on a example, to illustrate the sweetening power of the hydroxyl group, thioglycerol is much sweeter basis of odor, waving strength, and toxicity, these compounds in cold waving particularly, are far more desirable and effective than ammonium hydrogen sulfide, which has heretofore been utlized particularly for cold waving. Actually, not only do these non-polar mercaptans give better waving results and lack bad odor but also they are easier to remove from the hair and can be completely removed by shampooing or by thoroughly rinsing with water, no mal-odor being detected on the hair. More important is that their easy removal allows practically no retention by the hair to effect a relaxation or loosening of the permanent wave with each succeeding wetting of the hair.

This very important feature of not losing its curl, once the hair is waved, and the imparting of an excellent elasticity to the curl and a fine lustrous natural gloss, result in a more natural appearance than has been possible with prior hair waving treatments. Particularly effective are the mercaptans containing more than one water-solubiiizing group as, for example, the polyhydroxy mercaptan, e. g., thio-glycerol (glyceryl monomercaptan). This substances great value, on an equivalent SH basis is shown by the fact that it is several times as powerful in waving value as ammonium hydrogen sulfide.

As illustrations of waving solutions using the new waving agents according to this invention, the following specific examples are given:.

Example 1.Polar typeacidic Mercapto-acetic gms 10 Ammonium hydroxide cc 10 Water q. s. cc

Example 2.Non-polar tz/pe Glyceryl monomercaptan gms 5 Ammonium hydrpxide cc 2.5 Water q. s. cc 100 Example 3.-Polar type-basic Mercapto ethylamine gms.. 5 Water q. s. cc 100 The waying solution in any of the above examples may be utilized for effecting a cold wave by soaking the hair therein and applying thereafter a rinse, say, of sodium hypochlorite or other suitable rinse such as hydrogen peroxide, tartaric acid or the like. I have found that it is desirable to remove as much of the solution of the waving agent as possible by first rins- 7 ing with water.. I have discovered that with mercaptans containing water-solubilizing nonpolar groups, such as glyce'ryl monomercaptan, so complete is the removal by water alone that excellent non-relaxing waves can be obtained without the need for additional fixing or setting rinses.

In the examples given above the treatments resulted in satisfactory curls of medium tightness. For Example 1, however, the wave produced was not as strong as that given with the. waving solutions of Examples 2 and 3.

The hair treated with the solution of Example 3, which needed no ammonium hydroxide added,

did, however, tend to retain an odor noticeable upon wetting the hair while with the solution of Example 2 not a trace of bad odor was present even when the waved hair was re-wetted. For more effective washing'out of the mercaptocontaining amines from the hair, it is possible to have additional groups such as hydroxyl present. Particularly effective as such a compound is 2-hydroxy 3-amino propyl mercaptan.

' Thus it is seen that mercaptans containing polar and non-polar groups may be used. It has been brought out hereinbefore that either polar or non-polar groups are within the spirit and scope of this invention. Polar groups differ from non-polar in that in water solution they may ionize.

If any of the above examples are used for waving where heat is employed, the concentration of the waving agent may be materially decreased, approximately to one-third or one-fifth of the concentration given in the examples.

Thus, for waving where heat is employed, the concentrations of the waving agents given in the above examples, so decreased, would be:

Example 1.-lolar type-acidic Marcapto-acetic about 2 gms. to 3.3 gms.

Example 2.-Non-polar type Glyceryl monomercaptan, about 1 gm. to 1.66 gms.

Example 3.--Polar type-basic Mercapto ethylamine about 1 gm. to 1.66 gms.

In considering this invention, it must also be borne in mind that a purpose is to provide a waving agent for use in a solution, the concentration of the waving agent being much lower than heretofore effective commensurate with the desired effect of waving the hair.

As a comparison of the reduction of concentration of the waving ingredient provided by the instant invention as against that 'of one of the standard waving agents used in this art, namely, sodium sulfite, I have found that the same wave under the same conditions of procedure can be given with about one fifth of the concentration of our new waving agent, e. g., a solution of 2% of mercapto ethylamine will give the same effect as 15% of sodium sulfite. Thus, by the instant invention, I can use the same time of operation but greatly reduce the concentration of the waving ingredient. Alternately, I can shorten the time of waving by using a stronger concentration but still below the concentrations heretofore used, for instance the sodium sulfite above mentioned. I, therefore. provide a complete control of the waving process by the waving agent.

Utilizing the waving solution of any of the examples, the following procedure, or one similar thereto, may be employed in giving a permanent wave: The head of hair is blocked off into sections and each of the sectioned strands is then well soaked in the waving solution. Thereafter, each section of hair is wound on a mandrel to the form desired and heat is then applied, as by a chemical heating pad arranged over the wound section or by an electrical heating unit, the temperature being raised to about 212 F., and the hair, upon cooling, sets into its new configuration.

In giving a cold wave, procedures similar to the following, which may be variously modified, may be used: The head of hair is again sectioned of! into strands which are preferably wound on mandrels,. the waving solution being applied before or after winding by soaking the hair in any desired manner. After a suitable lapse of time for the reaction, the hair is water rinsed, and then a chemical rinse such as chlorine water may be applied which removes the last trace of the waving agent and thus assures the fixing of the hair in its new configuration, whereafter the hair will. have a permanent wave. With an easily -rinsable waving agent, such as glyceryl monomercaptan, this after rinse treatment is not necessary if proper water rinsing is employed.

I have found that in order to reduce the time of waving by this chemical method, i. e., without heat, to a figure comparable to the time of waving by heat it is necessary to increase the concentration of mercaptans in the waving solution about three to five times.

Thus, the concentrations of mercaptans in the above examples, when so increased from the concentrations suitable for waving with heat, would be as follows:

Example 1.-Polar type-acidic Mercapto-acetic about 6 gms. to 10 gms. Example 2.-Non-polar type Glyceryl monomercaptan, about 3 gms. to 5 gms.

to 8.3 gms.

Example 3.Polar type-basic Mercapto ethylamine, about 3 gms. to 5 gms. to

8.3 gms.

whether the fixation is by chemical, or by cooling subsequent to heating. But I do not under any conditions use concentrations higher than heretofore used. On the contrary, comparing the time-concentration factors of my novel waving agent with waving agents of the prior art for equivalent purposes, it will be found that under all analogous conditions I provide a distinct reduction in concentration while attaining optimum results in the final waving.

While throughout this specification I have specifically mentioned the wavingof hair, I do not wish to limit myself thereto, since by this invention it is possible to permanently alter or reform the form, shape or configuration of the hair as desired. Thus, my invention contemplates also the reverse of waving, such as de-kinking, removal of curls or waves, imparting of creases and the like. Furthermore, it is not my intention to limit this invention or the term hairl as used herein to treatment of human hair, but rather to include the treatment of any form of fiber structure which contains keratin. The waving solution according to this invention may be applied to the hair at any desired time, either before or after winding or otherwise mechanically placing the hair in its reformed desired shape or form and by any desired means, such as soaking, spraying, continuous circulation or-the like, and the claims are to be so construed. Furthermore, while I have described examples of our invention and have outlined advantages thereof over the prior art, I do not wish to limit myself to the exact materials or proportions given hereinbefore since a variety of like or similar materials may be used in lieu of those specified and the proportions thereof may be widely varied without departing from the spirit of my inven tion or the intended scope of the appended claims.

What I claim is:

1. A permanent waving composition comprising in solution a mercaptan having the general formula RSH, where the organic group R contains a carbon atom attached to the sulfur atom, said mercaptan having a hydroxyl substituent in the organic group R, in a solution containing an alkaline material having" a dissociation constant less than X10- said solution having a pH higher than pH 7 but nothigher than pH 9.5, the concentration of said mercaptan in terms of weight per volume ranging between about 1% and about the concentration of mercaptan and the pH of the solution being adjusted within said ranges to obtain a permanent change in the configuration of human hair during a given time of application without damage to the hair struc ture.

2. A composition according to claim 1 wherein the mercaptan is a mercapto-carbinol compound.

3. A composition according to claim 1 wherein the mercaptan is B-mercapto-ethyl alcohol.

4. A composition according to claim 1 wherein the mercaptan is mercapto-propanol.

5. A composition according to claim 1 wherein the mercaptan is a poly hydroxymercaptan.

6. A composition according to claim 1 wherein the mercaptan is thioglycerol.

'7. A composition according to claim 1 wherein the mercaptan is mono-thio-hexitol.

8. A composition according to claim 1 wherein the mercaptan is a mono-thio-polyoxyethylene glycol.

9. A permanent waving composition comprising a solution of ammonia and 1% to about 10% in terms of weight per volume of glyceryl monomercaptan, said solution having a pH ranging from about 9.2 to not higher than 9.5.

5 10. The method of permanently changing the configuration of human hair, including the steps of imparting the desired configuration to the hair and treating of the hair at a temperature tolerable to the human bodywith a permanent waving solution comprising an alkaline material having a dissociation constant less than 5 .10- and 1% to about-10% in terms of weight per volume of glyceryl mono-mercaptan, said solution having a pH higher than pH '7 and not higher than pH 9.5, the concentration of the mercaptan and the pH of the solution being adjusted within said ranges to obtain a permanent change in the configuration of human hair during a given time of application without damage to the hair structure; and then fixing said configuration.

11. The method of permanently changing the configuration of human hair, including the steps of imparting the desired configuration to the hair and treating of the hair at a temperature tolerable to the human body with a permanent waving solution comprising an alkaline material having a dissociation constant less than 5 10- and 1% to about 10% in .terms of weight per volume of a mercaptan containing a non-polar hydroxyl' group; said solution having a pH higher than pH 7 andnot higher than pH 9.5, the concentration of the mercaptan and the pH of the solution being adjusted within said ranges to obtain a, permanent change in the configuration of human hair during a given time of application without damage to the hair structure; and then fixing said configuration.

12. A composition according to claim 1 wherein the concentration is about 5%.

4 13. The permanent waving composition:

Glyceryl monomercaptan gms 5 Ammonium hydroxide cc 2.5 Water q. s. or

GOODRICH MCDONOUGH.

REFERENCES CITED The following references are of record in the 5 file of this patent:

J. Am. Med. Assn. (J. A. M. A.) June 15, 1935, "Thioglycerol Solution 1:50 (Abbott) pages 2186 and 2187, 167-59.. 

1. A PERNAMENT WAVING COMPOSITION COMPRISING A SOLUTION A MERCAPTAN HAVING THE GENREAL FORMULA R-SH, WHERE THE ORGANIC GROUP R CONTAINS A CARBON ATOM ATTACHED TO THE SULFUR ATOM, SAID MERCAPTAN HAVING A HYDROXYL SUBSTITUENT IN THE ORGANIC GROUP R, IN A SOLUTION CONTAINING AN ALKALINE MATERIAL HAVING A DISSOCIATION CONSTANT LESS THAN 5X10-3, SAID SOLUTION HAVING A PH HIGHER THAN PH 7 BUT NOT HIGHER THAN PH 9.5, THE CONCENTRATION OF SAID MERCAPTAN IN TERMS OF WEIGHT PER VOLUME RANGING BETWEEN ABOUT 1% AND ABOUT 10%, THE CONCENTRATION OF MERCAPTAN AND THE PH OF THE SOLUTION BEING ADJUSTED WITHIN SAID RANGES TO OBTAIN A PERMANENT CHANGE IN THE CONFIGURATION OF HUMAN HAIR DURING A GIVEN TIME OF APPLICATION WITHOUT DAMAGE TO THE HAIR STRUCTURE. 